US3320190A - Polyurethanes preparation utilizing piperidine compounds as catalysts - Google Patents

Polyurethanes preparation utilizing piperidine compounds as catalysts Download PDF

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Publication number
US3320190A
US3320190A US523269A US52326966A US3320190A US 3320190 A US3320190 A US 3320190A US 523269 A US523269 A US 523269A US 52326966 A US52326966 A US 52326966A US 3320190 A US3320190 A US 3320190A
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organic
catalysts
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reaction
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Allport Dennis Charlton
Gamlen George Albert
Corran John Anthony
Eaton David Crawford
Twitchett Harry James
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings

Definitions

  • tertiary amines vary considerbly in their suitability as catalysts for this reaction, some being much more active than others.
  • the catalytic activity of any particular amine cannot be accurately predicted since there is no simple relationship, for example, between catalytic activity and base strength. Structural factors, other than those which influence base strength, are believed to influence catalytic activity.
  • tertiary amines may be employed as catalysts although it is usually desirable to use those which have greatest eifect.
  • R which is attached to a carbon atom in the 3 or 4 position of the piperidine ring, represents a 2'-, 3'-, or 4'-pyridyl or a 1'-methyl-2-, l'-methyl-3'- or l'-methyl- 4-piperidyl radical.
  • the tertiary amines used in the process of the present invention may be made in good yield by known processes such as hydrogenation of bipyridyls to bipiperidyls which are subsequently methylated on the N atoms of the piperidyl nuclei to provide the catalyst, or by the hydrogenation of bipyridyls by methods whereby only one nucleus is reduced. Other suitable methods are described in the prior art.
  • the tertiary amines used in accordance with the present invention may be incorporated in polyurethane-forming reaction mixtures without ditficulty.
  • Their water-solubility is often such that they can be incorporated as aqueous solutions when used in polyurethane systems of which water is one of the ingredients.
  • organic solvents such as dipropylene glycol may be preferred. Because of their low volatility the amines are not unpleasant to use and do not confer undesirable odors upon the derived polyurethane products as do, for example, amines such as N-methylpiperidine.
  • tertiary amines suitable for use in the process of the present invention include 1,1-dimethyl- 4,4-bipiperidyl, 1-methyl-4(4'-pyridyl)piperidine, 1,1- dimethyl-4,3'-bipiperidyl, l,l'-dimethyl 4,2 bipiperidyl, l-methyl-4-(3-pyridyl)-piperidine and 1-methyl-3-(4-pyridyl) piperidine.
  • the tertiary amines are used in catalytic amounts, that is in amounts suflicient to catalyse the polyurethane reaction to a significant extent.
  • Suitable quantities are normally between 0.01% and 5% and preferably between 0.05% and 1.0% by weight of the organic polyhydroxy compound. The optimum proportions, however, will necessarily depend to a considerable extent upon the particular reaction components and conditions employed and may not always fall within the aforesaid normal ranges of proportions.
  • the catalysts of the present invention may, if desired, be used in the form of salts of weak acids.
  • Suitable weak acids are, for example, formic, acetic, lauric, methacrylic, oleic, oxalic, adipic, maleic, citn'c, phenylacetic, benzoic, salicyclic and terephthalic acids.
  • the amines may be used in the form of neutral salts, the amine and acid being present in equivalent proportions or, alternatively a deficiency or an excess of the acid may be used.
  • the tertiary amine salts may be added to the polyurethaneforming reaction mixture as such or, alternatively, the salts may :be formed in situ by adding the amine and the acid to the reaction mixture separately.
  • the starting materials to be used in the process of the present invention may be those fully described in the prior art relating to the manufacture of polyurethanes.
  • suitable organic polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, aromatic diisocyanates such as tolylene-2,4-diisocyanate, tolylene-Z,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3 methyldiphenylmethane 4 diisocyanate, mand p-phenylene diisocyanates, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4-diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, or diphenyl ether diisocyanate and cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate.
  • aromatic diisocyanates such as tolylene-2,4-diisocyanate,
  • Triisocyanates which may be used include aromatic triisocyanates such as 2,4,6-triisocyanatotoluene, and 2,4,4-triisocyanatodiphenylether.
  • aromatic triisocyanates such as 2,4,6-triisocyanatotoluene, and 2,4,4-triisocyanatodiphenylether.
  • suitable organic polyisocyanates comprise the reaction products of an excess of a diisocyanate with polyhydric alcohols such as trimethylolpropane and uretedione dimers and isocyanurate polymers of diisocyanates, for example, of tolylene-2,4- diisocyanate. Mixtures of polyisocyanates may be used.
  • suitable mixtures include mixtures of tolylene- 2,4- and 2,6-diisocyanates and the polyisocyanate compositions obtained by the phosgenation of the mixed polyamine reaction products of formaldehyde and aromatic amines such as aniline and orthotoluidine.
  • Suitable polyhydroxy compounds include hydroxyl group-containing polyesters, polyesteramides, polyethers and non-polymeric oxyalkylation products of active hydrogen-containing compounds.
  • the polyesters or polyesteramides may be made for example from dicarboxylic acids and polyhydric alcohols, and, as necessary, minor proportions of diamines or aminoalcohols.
  • Suitable dicarboxylic acids include succinic, glutaric, adipic, suberic, azelaic and sebacic acids as well as aromatic acids such as phthalic, isophthalic and terephthalic acids. Mixtures of acids may be used.
  • polyhydric alcohols include glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,3- butylene glycol, diethylene glycol, tetramethylene glycol, and 2,2-dimethyltrimethylene glycol.
  • polyhydric alcohls containing more than two hydroxyl groups per molecule may be used, for example trimethylolpropane and other hexanetriols, trimethylolethane, pentaerythritol and glycerol. Such compounds are included in varying amounts according to the desired rigidity of the polyurethane products.
  • polyhydric alcohols and dicarboxylic acids there may also be reacted compounds containing more than two groups selected from hydroxyl, carboxyl and secondary and primary amino groups, of which examples include diethanolamine, trimesic acid, dihydroxystearic acid and tricarballylic acid.
  • polyesteramides examples include ethylene diamine, hexamethylene diamine, monoethanolarnine, phenylene diamines and tolylene diamines.
  • polyesters and polyesteramides normally have molecular Weights of from 200 to 5000, with predominantly primary hydroxyl end groups.
  • polyethers for use in the production of the polyurethane materials there may be mentioned hydroxyl-ended polymers and co-polymers of cyclic oxides, for example 1,2-alkylene oxides such as ethylene oxide, epichlorohydrin, 1,2-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, oxacyclobutane and substituted oxacyclobutanes, and tetrahydrofuran.
  • Such polyethers may be linear polyether glycols as are prepared, for example by the polymerisation :of an alkylene oxide in the presence of a basic catalyst such as potassium hydroxide and a glycol or a primary monoamine.
  • branched polyethers prepared for example by the polymerisation of an alkylene oxide in the presence of a basic catalyst and a substance having more than two active hydrogen atoms per molecule, for example ammonia, hydrazine and polyhydroxy compounds such as glycerol, trimethylolpropane and other hexanetriols, trimethylolethane, triethanolamine, pentaerythritol, sorbitol, sucrose and phenol-formaldehyde reaction products, aminoalcohols such as monoethanolamine and diethanolamine, and polyamines such as ethylene diamine, tolylene diamine and diaminodiphenylmethane.
  • Branched poly- for example by the polymerisation of an alkylene oxide in the presence of a basic catalyst and a substance having more than two active hydrogen atoms per molecule, for example ammonia, hydrazine and polyhydroxy compounds such as glycerol, trimethylolpropane and other hexanetriol
  • ethers may also be produced by copolymerising a cyclic oxide of the type already mentioned with cyclic oxides having a functionality greater than two, for example diepoxides, glycidol and 3-hydroxymethyloxacyclobutane.
  • the polyethers normally have molecular weights of from 200 to 8000. Mixtures of linear and branched polyethers may be used if desired.
  • the non-polymeric oxyalkylation products of active hydrogen-containing compounds which may be used in the production of the polyurethane materials are polyhydroxy compounds in which the degree of oxyalkylation is insufficiently high for the compounds to contain a plurality of ether groups.
  • the non-polymeric oxyalkylation products of primary and secondary polyamines such as, for example, the reaction products of tolylene diamine with up to 5 moles per mole of alkylene oxide.
  • Mixtures of polyhydroxy compounds may be used if desired.
  • the foam-forming gas may be generated by a variety of methods.
  • the gas may be carbon dioxide generated by the reaction of a proportion of the organic polyisocyanate with water incorporated in the reaction mixture.
  • the gas may be generated by incorporating in the reaction mixture a suitable low boiling liquid which, when the reaction mixture heats or is heated above the boiling point of the said liquid, volatilises to give the foam forming gas. Combinations of methods, for example of the above two methods, may be used.
  • Water is usually employed in amounts of from 1% to 10% by weight of the polyhydroxy compound when used as a gas-generating agent.
  • Suitable low boiling point liquids are liquids that are inert towards the polyurethane foam-forming ingredients and have boiling points not exceeding 75 C. at atmosheric pressure and preferably between -40 C. and 50 C.
  • halogenated hydrocarbons such as methylene chloride, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, m'onochlorodifluoromethane, dichlorotetrafluoroethane, l,1,2-trichloro-l,2,2-trifluoroethane, dibromodifluoromethane and monobromotrifiuoroethane.
  • Such liquids are usually employed in amounts of from 1% to preferably 5% to 50% by weight of the polyhydroxy compound.
  • the preparation of the foamed, cellular polyurethanes may be carried out by the general methods fully described in the prior art.
  • the materials may be mixed continuously or discontinuously and the organic polyhydroxy compound may be first reacted with a part or the whole of the organic polyisocyanate before the final reaction to give a foam is carried out in a second stage.
  • This convenient one-stage process cannot always be satisfactorily carried out with all organic polyhydroxy compounds. In particular those compounds containing predominantly secondary hydroxyl groups do not normally give satisfactory foam using a one-stage process unless particular catalysts are employed.
  • Examples of predominantly secondary hydroxyl groupcontaining polyhydroxy compounds include polyesters and polyesteramides prepared from an excess of polyhydric alcohol and amino compounds over dicarboxylic acid, wherein the polyhydric alcohol contains secondary hydroxyl groups, for example propylene glycol, 1,3-butylene glycol or glycerol.
  • Secondary hydroxyl-ended polyethers include polymers and copolymers of substituted 1,2-alkylene oxides such as propylene and butylene oxides. It is preferred to use predominantly secondary hydroxyl-ended polymers of propylene oxide, especially those with molecular weights of from 400 to 6000.
  • the tertiary amines proposed herein can usually be employed at lower concentrations than the tertiary amine catalysts previously proposed. Furthermore the derived foams are characterized by more rapid surface cure than foams made with other tertiary amine catalysts such as triethylene diamine.
  • tertiary amines herein proposed as catalysts are extremely effective and may be used as the sole catalytic entity in polyurethane-forming systems it is common practice especially in the production of foamed poly urethanes to employ more than one catalyst.
  • one or more tertiary amines in conjunction with an organic compound of a metal.
  • Organic metal compounds which may be used include tin compounds, for example stannous octoate, dibutyltin dilaurate and dibutyltin diacetate, lead compounds, for example, lead acetate and lead octoate and coordination compounds of the transistion metals, for example, the acetylacetonates of iron and manganese.
  • tertiary amines amy be used together with the tertiary amines proposed herein, optionally in the presence of an organic metal compound.
  • suitable tertiary amines include triethylamine, dimethylethylamine, dimethylbenzylamine, dimethylcyclohexylamine, dimethylphenylethylamine, tetramethyl 1,3 butanediamine, triethylene diamine, N-akyhnorpholines, N-alkylpyrrolidines, N-alkylpiperidines, N-(fi-dimethylaminoethyl)-N'-methylpiperazine, pyrrolizidine, fi-dimethylaminopropducnide and fully N-substituted 4-aminopyri dines such as 4-dirnethylaminopyridine.
  • Amine salts such as dimethylbenzylamine lactate are also suitable.
  • the general methods of preparation of polyurethanes may include the incorporation in the polyurethane-forming mixture of various additives such as surface-active agents, for example oxyethylated fatty alkyl phenols, oxyethylated fatty alcohols, salts of sulphuric acid derivatives of high molecular weight organic compounds and alkyl and aryl polysiloxanes and copolymers thereof with alkylene oxides, foam-stabilising agents, for example ethyl cellulose, colouring matters, plasticisers, fire-proofing agents, for example tris-2-chloroethylphosphate and tris-2,3-dibr0mopropyl phosphate and antioxidants.
  • additives such as surface-active agents, for example oxyethylated fatty alkyl phenols, oxyethylated fatty alcohols, salts of sulphuric acid derivatives of high molecular weight organic compounds and alkyl and aryl polysiloxa
  • R has the significance hereinbefore stated with one molecular proportion of a compound of the general formula R'X Where R represents an alkyl, cycloalkyl or aralkyl radical and X represents an atom or group capable of ionising to form the anion of the quaternary ammonium salt.
  • the compound R'X is preferably an alkyl, cycloalkyl or aralkyl halide, particularly a chloride or bromide but it may also be an alkyl sulphate, particularly methyl or ethyl sulphate.
  • the quarternary ammonium salts may be prepared by the general methods described in the prior art for such reactions.
  • the tertiary amine and the compound R'X may be reacted together in the proportions stated, at normal or elevated temperatures, optionally in the presence of a solvent for the reactants.
  • the products are monoquaternary ammonium salts containing a tertiary nitrogen atom may be used as catalysts in polyurethane processes using the general methods described in the prior art and particularly those hereinbefore described with reference to the tertiary amines from which the quaternary ammonium salts are derived. They are of particular value in processes where a water-soluble catalyst of low volatility is required.
  • Example 1 To 100 parts of an oxypropylated glycerol of molecular weight approximately 3000 and hydroxyl value 56 mg. KOH/ g. is added 0.5 part of stannous octoate. To this mixture is then added 3.8 parts of a solution comprising 2.9 parts of water, 0.8 part of a siloxane-oxyalkylene copolymer and 0.1 part of 1,1-dimethyl-4,4'-bipiperidyl. 38 parts of an :20 mixture of tolylene-2,4 and 2,6- diisocyanates are rapidly stirred into the blend and the mixture is poured into a mould. A foam forms which cures to give a resilient cellular product having low density and good structure.
  • Example 2 If in the foregoing Example 1 the 1,1'-dirnethyl-4,4'- bipiperidyl is replaced by an equal weight of 1-methyl-4- (4-pyridy1)piperidine a resilient cellular product of low density and good structure is similarly obtained.
  • Example 3 If in the foregoing Example 1 the 1,1-dimethyl-4,4'- bipiperidyl is replaced by an equal weight of 1,l'-dimethyl-4,2-bipiperidyl a resilient cellular product of low density and good structure is similarly obtained.
  • Example 4 If in the foregoing Example 1 the 1,1'-dimethyl-4,4'- bipiperidyl is replaced by an equal weight of l,1'-dimethyl-3,2'-bipiperidyl a resilient cellular product of low density and good structure is similarly obtained.
  • Example 5 parts of oxypropylated glycerol of molecular weight approximately 3000 are continuously blended with 44.7 parts of an 80:20 mixture of tolylene-224- and 2:6-diisocyanates, 0.3 part of stannous octoate, 3.5 parts of water, 1.0 part of a siloxane-oxyalkylene copolymer, and 0.075 part of 1,1-dimethyl-4,4-bipiperidyl and the liquid mixture dispensed on to a moving mould.
  • a length of approximately 30 ft. is continuously produced, the foam having excellent stability during processing.
  • the resultant flexible foam is of fine even texture and has good physical properties.
  • Example 6 A mixture comprising 100 parts of oxyproplated tri methylolpropane (hydroxyl value 540 mg. KOH/g.), 2 parts of water, 15 parts of triethanolamine, 38 parts of trichlorofiuoromethane, 3 parts of a siloxane-oxyalkylene copolymer and 4 parts of a solution comprising 2 parts of 1,1'-dimethyl-4,4-bipiperidyl and 2 parts of dipropylene glycol is prepared and then rapidly mixed with 230 part of a diisocyanatodiphenylmethane composition. The mixture is poured into a mould and after 1 minute a rigid foam is obtained with a tack-free surface.
  • oxyproplated tri methylolpropane hydroxyl value 540 mg. KOH/g.
  • Example 8 A mixture comprising 50 parts of oxypropylated tolylene diamine (hydroxyl value 480 mg. KOH/g.), 50 parts of oxypropylated triethanolamine (hydroxyl value 520 mg. KOH/g.), 30 parts of tris-2-chloroethy1 phosphate, 2 parts of water, 3 parts of a siloxane-oxyalkylene copolymer, 33 parts of trichlorofluoromethane and 2 parts of a solution comprising 1 part of 1,1'-dimethyl-4,4'-bipiperidyl and 1 part of dipropylene glycol is prepared. and then rapidly mixed with 168 parts of a diisocyanatodiphenylmethane composition. The mixture is poured into a mould and after 90 seconds a rigid foam is obtained with a tack-free surface.
  • Example 9 10 parts of a polyester prepared from 64 parts of adipic acid, 51 parts of diethylene glycol and 2.3 parts of pentaerythritol having an acid value of 2.9 mg. KOH/g, a hydroxyl value of 76 mg. KOH/ g. and a viscosity of 93 poises at 25 C. are stirred with 0.05 part of 1,1'-di methyl-4,4-bipiperidyl. 0.95 part of tolylene diisocyanate is then stirred in rapidly and the resultant mixture sets to a non-flowing rubbery composition within 2 minutes. If the 1,1-dimethyl-4,4-bipiperidyl is omitted from the above composition the mixture still remains as ,a viscous syrup after 1 hour.
  • Example 10 100 parts of a polyester prepared from 228 parts of adipic acid, 177 parts of diethylene glycol and 8.16 parts of pentaerythritol having an acid value of mg. KOH/g., a hydroxyl value of 67 mg. KOH/ g. are mixed with 62 parts of a 65:35 mixture of tolylene-2,4- and 2,6-diisocyanates. To this mixture is added with vigorous agitation an activator mixture consisting of 5 parts of water, 0.2 part of 1,1'-dimethy1-4,4'vbipiperidyl, 1 part of a.
  • a process for the manufacture of polyurethane materials which comprises reacting an organic polyisocyanate with an organic polyhydroxy compound in the presence of a catalytic amount of a tertiary amine of the general formula:
  • R which is attached to a carbon atom in the 3 or 4 position, represents a 2'-, 3'- or 4'-pyridyl or a 1- methyl-2-, 1'-methyl-3- or 1'-methyl-4'-piperidyl radical.
  • organic polyhydroxy compound is selected from the group consisting of hydroxyl group-containing polyesters, and hydroxyl polyethers.
  • tertiary amine is used in conjunction with an organic compound of a metal selected from the group consisting of stannous octoate, dibutyltin dilaurate and lead octoate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Pyridine Compounds (AREA)
US523269A 1965-02-03 1966-01-27 Polyurethanes preparation utilizing piperidine compounds as catalysts Expired - Lifetime US3320190A (en)

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Application Number Priority Date Filing Date Title
GB4682/65A GB1131301A (en) 1965-02-03 1965-02-03 Polyurethanes
GB1410465 1965-08-11
GB468266 1966-01-19
GB3436765 1966-01-19

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US (1) US3320190A (enrdf_load_stackoverflow)
BE (1) BE675966A (enrdf_load_stackoverflow)
DE (1) DE1595823A1 (enrdf_load_stackoverflow)
DK (1) DK113885B (enrdf_load_stackoverflow)
GB (1) GB1131301A (enrdf_load_stackoverflow)
NL (1) NL6601199A (enrdf_load_stackoverflow)
SE (1) SE312682B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897396A (en) * 1973-11-06 1975-07-29 Bridgestone Tire Co Ltd With substituted benzoic acid catalysts accelerating the cure of polyurethaneureas
EP0068454A1 (en) * 1981-07-01 1983-01-05 Takeda Chemical Industries, Ltd. Composition for polyurethane resins and production of the resins
US4450246A (en) * 1982-10-26 1984-05-22 W. R. Grace & Co. Novel polyurethane catalysts in polyurethane foam process
US11557335B2 (en) 2020-07-07 2023-01-17 International Business Machines Corporation Erasing a partition of an SRAM array with hardware support

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3109825A (en) * 1959-02-27 1963-11-05 Ici Ltd Manufacture of polyurethane materials

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3109825A (en) * 1959-02-27 1963-11-05 Ici Ltd Manufacture of polyurethane materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897396A (en) * 1973-11-06 1975-07-29 Bridgestone Tire Co Ltd With substituted benzoic acid catalysts accelerating the cure of polyurethaneureas
EP0068454A1 (en) * 1981-07-01 1983-01-05 Takeda Chemical Industries, Ltd. Composition for polyurethane resins and production of the resins
US4450246A (en) * 1982-10-26 1984-05-22 W. R. Grace & Co. Novel polyurethane catalysts in polyurethane foam process
US11557335B2 (en) 2020-07-07 2023-01-17 International Business Machines Corporation Erasing a partition of an SRAM array with hardware support

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SE312682B (enrdf_load_stackoverflow) 1969-07-21
DE1595823A1 (de) 1970-02-12
DK113885B (da) 1969-05-05
NL6601199A (enrdf_load_stackoverflow) 1966-08-04
GB1131301A (en) 1968-10-23
BE675966A (enrdf_load_stackoverflow) 1966-08-02

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